Sulfuric acid esters of hydroxyalkylamino-anthraquinones



Patented Feb. 4, 1947 7 T UNITED STATES PATENT OFFICE SULFURIC ACID ESTERS F HYDROXY- ALKYLAMINO-ANTHRAQUINONES William Wyndham Tatum, Blackley, Manchester,

England, assiginor to Imperial ilhemical Industries Limited, a corporation of Great Britain No Drawing. Application May 3, 1943, Serial No. I

485,515. In Great Britain May 11, 1942 v, 2 Claims. (01. 260379). 1 2

This invention relates to the manufacture of Example 1 new anthraquinone dyestuffs useful for dyeing wool.

According to the invention we provide a process for the manufacture of the new dyestuffs 5 which comprises treating with an agent adapted to convert aminoalcohol derivatives into their acid sulphuric esters a l-aminoanthraquinone derivative which carries in the 4-position a sub- 15 parts of 2-chloro-1-amino4-c-hydroxyisopropylaminoanthraquinone and 30 parts of sodium pyrosulphate are stirred with 100 parts of pyridine and heated at 80-100 C. for 1-2 hours. Water and 15 parts of sodium carbonate are added and the pyridine is steamed off. The soobtained violet solution is filtered from insoluble matter, and the dyestufi is precipitated from the stltuent of the general formula filtrates by addition of sodium chloride. It con- CHQR sists of the sodium salt of the acid sulphuric ester of 2-chlor0-1-amino-4- e hydroxyiscpropylami- ROE noanthraquinone and dyes wool from an acid bath in bright bluish-violet shades. The dyestufi where R may be hydrogen or an alkyl Tadmal is of special value in view of its very good leveland R is an alkylene radical, and which may also 1m d penetrating properties.

carry in the 2-position another simple substituh 2-ch1'0ro-1-amin0-4- B hydroxyisoprop e p a chlorine or a bromine atom aminoanthraquinone used in this example is oba e yl o p tained as follows:

The l-aminoanthraquinone derivatives which 60 parts of 1 4 ..1 aminoanthmare to be converted into their acid sulphuric esters quinone, 15 parts f potassium carbonate, 7.5 are made, for example, by interacting a l-aminoparts of pgtasgium c tate and 1 part of copper anthraquinone containing in the 4-position an acetate are added to 240 parts of nitrobenzene exchangeable atom or group such as halogen or and 90 parts of Z-amino-n-propanol, and the alkoXy t a al p a c hydroXyamine 0f the mixture is heated at IOU-120 C. for 16 hours. a1 formula When cold, the crystals of 2-chloro-1-amino--fl- OHzR hydroxyis'opropylaminoanthraquinone are filtered NHLCH off, washed with ethanol and with water and I r dried. The crystals are dark violet in colour, R OH have M. P. 221-222 0. and give a bluish-violet where R and R have the significance hereinbesolution in ethylene glycol monoethyl ether. Analfore ascribed thereto. As aliphatic hydroxyysis: Found N 8.45%; C1 10.5%. CnHtsOsNzCl amines there may be instanced 2-aminopropanol, required N 8.46%; Cl 10.75%. 3-amino-2-butanol and B-aminQ-Z-methyl-butanol. Alternatively, the l-amino group may be 7 Example 2 introduced into an anthraquinone, which already contains the aliphatic hydroxyamine substituent in the it-position, as by reduction of 2. nitro group or by hydrolysis of an acetylamino or a benzoylamino group.

The conversion into the acid sulphuric acid esters is carried out in known manner, for ex- The u 8 hydroxyisopropylamino g ample with Sulphuric i fuming .sulphuric methylanthraquinone used in this example is obacid or chlorosulphonic acid, or with a pyrosultamed as follows:

phate in presence of a tertiary base such as pyri- 36 parts f 4 brom0 1 amin0 2 methy1anthm dine. The acid sulphuric esters are conveniently quinone 9 parts f potassium carbonate, 5 parts isolated as alkah metal or ammomum saltsof potassium acetate, 0.5 part of copper acetate,

on W001 the new dyestuffs glve Very bnght 140 parts of nitrobenzene and 45 parts of Z-ami- Shades avi V y good levelling Properties and no-n-propanol are stirred together at a temperaood fastnes p op t e including fastness to ture of 105-125" c. for 16 hours, the mixture is ht. cooled, and the crystals which separate are col- The invention is illustrated but not limited by lected by filtration. The crystals are washed with the following examples, in which the parts are ethanol and water, and then dried. They consist expressed by weight. of 1amino-4-B-hydroxyisopropylamino-Z-meth- 1-amino-4-fl-hydroxyisopropylamino-2 methylanthraquinone is converted into the sodium salt of its acid sulphuric ester by the method set 40 forth in Example 1. It dyes wool from an acid bath in bright violet shades of excellent levelling properties.

ylanthraquinone and have M. P. 223225 C. Analysis: Found N 9.15%. CmHmOsNa requires N9.04%.

Example 3 42 parts of 2-bromo-1-amino-4p-hydroxyisopropylaminoanthraquinone and '70 parts of sodium pyrosulphate are introduced into 300 parts of pyridine and heated at 90 C. for 2 hours. The melt is then poured into an aqueous solution of 40 parts of sodium carbonate and the pyridine removed by steam distillation. The violet solution is filtered and the dyestuff precipitated from the filtrates by the addition of sodium chloride. It consists of the sodium salt of the acid sulphuric ester of 2-bromo-1-amino-4-;3-hydroxyisopropy1- aminoanthraquinone and dyes wool in bright bluish-violet shades of very good levelling properties.

The 2-bromo-1-amino-4- p hydroxyisopropylaminoanthraquinone used in this example is obtained by condensing at 90-100 C. '76 parts of 2:4-dibromo 1 aminoanthraquinone with 100 parts of Z-aminopropanol in 240 parts of nitrobenzene in the presence of 38 parts of potassium acetate and parts of cuprous chloride. When isolated as described in Example 2 it is obtained in the form of violet crystals, M. P. 201 C. These, when recrystallised from nitrobenzene have M. P. 208 C.

Example 4 5.5 parts of Z-methyl-l-amino--(afi-dimethyl- -hydroxypropylamino) -anthraquinone are dissolved in 30 parts of pyridine and 11 parts of sodium pyrosulphate are added. The mixture is stirred at 85 C. for 2 hours. Water and 6 parts of sodium carbonate are then added and the pyridine is removed by distillation in steam. The residual liquid is filtered to remove insoluble matter and the dyestuif is precipitated from the 11- trate by addition of sodium chloride. The sodium salt of the acid sulphuric ester of 2-methyll-amino-l- (ocfidimethyl y hydroxypropylamino)-anthraquinone is obtained as a bluish-black powder which dissolves in water to give a violet solution from which it is precipitated by addition of hydrochloric acid or caustic soda. It dyes wool in violet shades from an acid bath.

The v 2-methyl-1-amino-4-(aB-dimethyl-y-hydroxypropylamino) -anthraquinone used in the above example is obtained as follows:

A mixture of 10 parts 4-bromo-1-amino-2- methylanthraquinone, 0.25 part cuprous chloride, 3.3 parts potassium acetate, 20 parts pyridine and 20 parts 3-a mino-2-methylbutanol is stirred at a temperature of 90-100 C. for 20 hours and the resultant deep violet solution is freed from pyridine by distillation in steam. The 2-methyl- 1-amino-4-(ap-dimethyl 'y hydroxypropylamino)-anthraquinone is isolated from the residual liquid by filtration.

Example 5 20 parts of Z-bromo-l-aminol-p-hydroxyisopropylaminoanthraquinone are dissolved in 150 parts of sulphuric acid and the solution is stirred at 20 C. for 1 hour. It is then poured into 1500 parts of ice and Water containing parts of caustic soda and the resultant mixture is filtered. The solid obtained is the sodium salt of the acid sulphuric ester of 2-bromo-1-amino-4- p-hydroxyisopropylaminoanthraquinone. It is washed with 2% brine and dried. It is identical with the dyestufi of Example 3. In place of the 100% sulphuric acid used in thi example, there may alternatively be employed weaker acid for example of 96% strength, or there may be used fuming sulphuric acid containing about 5% of sulphur trioxide.

I claim:

1. The sulfuric acid esters of the compounds having the formula:

NHs

NH.CH

CH R

00 g o1 6 /CHs NH-CH CH2OH WILLIAM WYNDHAM TATUM.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,717,809 Reddelien et al June 18, 1929 2,022,956 Dreyfus Dec. 3, 1935 1,688,553 Olpins Oct. 23, 1928 FOREIGN PATENTS Number Country Date 447,037 British Ma 4, 1936 131,509 Swiss Feb. 15, 1929 176,930 Swiss May 15, 1935 210,734 Swiss July 3, 1940 183,883 Swiss Apr. 30, 1936 41,728 Dutch Oct. 15, 1937 473,762 British Oct. 18, 1937 

